The instant invention covers compounds having the generic structure: ##STR4## wherein the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond; wherein X represents the moieties: ##STR5## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.8 and R.sub.9 represent hydrogen or methyl with the provisos that (i) at least three of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 represent hydrogen and (ii) when the dashed line is a carbon-carbon single bond and X is: ##STR6## then one of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 is methyl and the other represents hydrogen; wherein R.sub.5 represents hydrogen, MgZ or Li; wherein Z represents chloro, bromo or iodo; and wherein R.sub.6 represents hydrogen or methyl; as well as uses of the above compounds, with the exception of the organometallic compounds of the genus, for augmenting or enhancing the aromas and/or taste of consumable materials.
Materials which can provide minty, camphoraceous, dry woody, sweet, fruity, woody, patchouli, green, herbaceous, basil-like, citrus-like, strong ambery, vanoris-like, bergamot-like, lime-like, grapefruit-like, peppery, precious-woody, vetiver-like, fresh, musky, lavender, thyme, rosemary, sweaty, rooty, carrot-like, beet-like and earthy aromas with floral, citrus, lavender and amber topnotes and backgrounds are known in the art of perfumery. Many of the natural materials which provide such fragrances and contribute desired nuances to perfumery compositions are high in cost, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products.
By the same token, materials which can provide oriental, incense-like peppery, blueberry-like, eucalyptol-like, minty, camphoraceous, sage-like, grapefruit-like, floral, musk-like, rose-like, black pepper, spicy, patchouli, cooling, menthol-like, sandalwood-like, woody, earthy and walnut-like aromas with oriental, black pepper, peppery, minty, menthol-like, sage-like, grapefruit-like, eucalyptol-like, camphoraceous, floral, rosey, earthy and patchouli-like tastes are well known in the art of flavoring for foodstuffs, toothpastes, chewing gums and medicinal products. Many of the natural materials which provide such flavor nuances and contribute desired nuances to flavoring compositions are high in cost, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products.
Sweet, fruity, berry-like, cooling, woody and floral aroma and taste nuances are known in the art of the production of smoking tobaccos and smoking tobacco articles. Many of the natural materials which provide such aroma and taste nuances to smoking tobacco compositions are high in cost, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products.
There is, accordingly, a continuing effort to find synthetic materials which will replace, enhance or augment the essential flavor and/or fragrance notes provided by natural essential oils or compositions thereof. Unfortunately, many of these synthetic materials either have the desired nuances only to a relatively small degree or else contribute undesirable or unwanted odor to the consumable compositions. The search for materials which can provide more refined patchouli-like aromas, for example, have been difficult and relatively costly in the areas of both natural products and synthetic products.
Artificial flavoring agents for foodstuffs have received increasing attention in recent years. For many years such food flavoring agents have been preferred over natural flavoring agents at least in part due to their diminished cost and their reproducible flavor qualities. For example, natural food flavoring agents such as extracts, concentrates and the like are often subject to wide variations due to changes in quality, type and treatment of the raw materials. Such variations can be reflected in the end products and result in unfavorable flavor characteristics in said end product. Additionally, the presence of the natural product in the ultimate food may be undesirable because of increased tendency to spoil. This is particularly troublesome in food and food uses where such products as dips, soups, chips, sausages, gravies and the like are apt to be stored prior to use.
The fundamental problem in creating artificial flavor agents is that the artificial flavor to be achieved be as natural as possible. This generally proves to be a difficult task since the mechanism for flavor development in many foods, medicinal products, chewing gums and toothpastes is not completely known. This is noticable in products having licorice, citrusy and vegetable flavor characteristics particularly.
Even more desirable are producet that can serve to substitute for difficult-to-obtain natural perfumery oils and at the same time substitute for natural flavoring ingredients in foodstuffs, chewing gums, medicinal products, toothpastes, and smoking tobaccos.
Oxobicyclo compounds are known in the prior art. Thus, Nagakura, et al, Bull. Chem. Soc. Japan Vol. 48(10), 2295-6 (October 1975) discloses the compound defined according to the generic structure: ##STR7## wherein one of R.sub.1 ', R.sub.2 ', R.sub.3 ' or R.sub.4 ' is methyl and the others represent hydrogen. In addition, Conia and Rouessac, Bull. Soc. Chem. France 1953 (page 1925 et seq.) discloses processes for producing oxobicyclo compounds according to the following reaction steps: ##STR8##
The use of oxotricyclic derivatives in perfumery is disclosed in U.S. Pat. No. 3,996,169, issued on Dec. 7, 1976. Thus, in U.S. Pat. No. 3,996,169, a genus defined according to the structure: ##STR9## is disclosed, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10 is selected from the group consisting of hydrogen and methyl; and wherein the dashed line may be a carbon-carbon single bond or a carbon-carbon double bond. Members of this genus are indicated to be capable of altering, modifying, enhancing or emparting an aroma of or to consumable materials including colognes, perfumes and perfumed articles and such an aroma is of a patchouli type.
Arctander, "Perfume and Flavor Chemicals", 1969, Vol. 1 discloses the use in perfume compositions and foodstuff flavors of "decalinol", "decalone", "fenchone", and "fenchyl alcohol", thusly:
"(i) 1385: FENCHONE laevo-Fenchone. (dextro- is known but less common as a fragrance material). PA1 1,3,3-Trimethyl-2-norbornanone. PA1 1,3,3-Trimethyl bicyclo-1,2,2-heptone-2. ##STR10## Warm-camphoraceous, powerful and diffusive, basically sweet odor. Warm, somewhat burning and bitter taste with a medicinal note. PA1 (ii) 1387: FENCHYL ALCOHOL PA1 1,3,3-Trimethyl-2-norbornanol. PA1 1,3,3-Trimethyl bicyclo-1,2,2-heptanol-2. PA1 2-Fenchanol. PA1 Fenchol. ##STR11## The racemic alpha-Fenchol has a somewhat lower melting point, and the beta-Fenchols are all liquid at room temperature. PA1 Fenchol made by reduction of Fenchone from Cedarleaf oil is usually a mixture of several isomers, including the crystalline alpha-isomers. The beta-isomer forms a crystalline Hydrate which may be solid at room temperature. PA1 This interesting alcohol (or mixed alcohols) finds use in perfume compositions ranging from woody or herbaceous to Citrus-Lime and even certain floral types. It produces power and `lift` to floral fragrances, and solid background to Lime and other Citrus bases, having the advantage over the Terpenes in being very stable in soap. PA1 Fenchyl alcohol is also used in flavor compositions such as Strawberry and other berries, Lime and Spice, etc. PA1 (iii) 824: TRANS-DECAHYDRO-BETA-NAPHTHOL PA1 trans-beta-Decanol. PA1 (sometimes called "Decalinol".) PA1 Bicyclo-4,4,0-Decanol ##STR12## Colorless viscous liquid, solidifying in the cold to an open mass. The presence of variable amounts of the cis-isomer is mainly responsible for the variations in physical appearance of this material. PA1 Mild, sweet, slightly camphoraceous-woody, also warm and mildly spicy odor of fair tenacity. The odor has been compared to that of Dihydrocarveol, but such description does not help many perfumers. PA1 Practically insoluble in water, soluble in alcohol and oils. PA1 This alcohol has been used, and is still used on a modest scale, in perfume compositions, mostly in connection with woody and camphoraceous fragrance types, including the Ionones, Cyclohexylderivatives, etc. Several of its esters (see following monographs) have been more successful as perfume materials). PA1 However, since the Ambregis- and Sandalwood-notes, which are represented to a certain degree in the esters, can be obtained with much superior beauty by way of modern perfume chemicals, there is reason to believe that the Decahydronaphthyl series will eventually become obsolete. PA1 Prod.: by catalytic hydrogenation of beta-Naphthol. The reaction yields a mixture of cis- and trans-isomers, but the perfumers generally prefer the trans-isomer or a material primarily consisting of that isomer. PA1 (iv) 830: BETA-DECALONE PA1 Decahydro naphthalone PA1 The commercial products consist of a mixture of cis- and trans-isomers. ##STR13## Viscous colorless liquid, solidifying in the cold. Practically insoluble in water, soluble in alcohol and oils. PA1 The cis-isomer is liquid and boils at 247.degree. C. PA1 The trans-isomer is solid below 6.degree. C. and boils at 241.degree. C. PA1 Semi-dry, tenacious odor resembling part of the Ambregris-picture, also woody, remotely reminiscent of Sandalwood. Odor variations are observed in materials from different sources of supply. PA1 This ketone has found a little use in perfume compositions, including soap perfumes, where it can introduce pleasant background notes in support of Musk Ambrette, Labdanum, Methylionones, etc. PA1 Recent development in Ambregris chemicals has brought much superior materials in the hands of the perfumer, and it is very likely that the title material, and many of its relatives, will become obsolete within the next decade or so. PA1 Prod.: by oxidation of beta-Decalol with Chromic acid mixture."
This ketone finds some use as a masking odor in industrial fragrances. It is also used in the reconstruction of Fennel oil and a few other essential oils.
In spite of its rather unpleasant taste, it is used in various Berry complex flavors, in Spice complexes and in certain types of Liquer flavoring.
The concentration used is about 0.1 to 5 ppm in the finished product.
Almost insoluble in water, soluble in alcohol, micsible with oils. Powerful and diffusive, Camphor-like, but sweeter and more Citrus-like almost Lime-like odor with more or less of an earthy-dry character, according to the composition and isomer-ratio.
The taste is somewhat bitter-Lime-like, camphoraceous and slightly woody-musty.
The concentration is normally low, e.g. 0.2 up to 5 ppm in the finished product.
U.S. Pat. No. 3,932,515 discloses the use of the compound having the structure: ##STR14## in perfumery and specifically indicates that such compound has a woody aroma of high tenacity. U.S. Pat. No. 3,932,516 discloses the compound having the structure: ##STR15## and indicates that this compound is useful in perfumery due to its woody character.
None of the references cited above, or for that matter any other references discloses compounds which have a close structural relationship to the genus of compounds of the instant invention. In any event, the organoleptic properties of the compounds of the references are different in kind from those of the compounds of the instant invention.